CN106349209A - Process for synthesizing heliotropin - Google Patents
Process for synthesizing heliotropin Download PDFInfo
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- CN106349209A CN106349209A CN201610720464.9A CN201610720464A CN106349209A CN 106349209 A CN106349209 A CN 106349209A CN 201610720464 A CN201610720464 A CN 201610720464A CN 106349209 A CN106349209 A CN 106349209A
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- CN
- China
- Prior art keywords
- heliotropin
- temperature
- kettle
- piperonyl cyclonene
- acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
- C07D317/54—Radicals substituted by oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a process for synthesizing heliotropin. The process for synthesizing heliotropin comprises the following steps: synthesizing, oxidizing, thereby obtaining the heliotropin. The production process is simple, easy to operate, low in energy consumption, low in cost, high in efficiency and suitable for popularization, and the heliotropin produced by the process disclosed by the invention has the yield of about 87%.
Description
Technical field
The present invention relates to chemosynthesis technical field is and in particular to a kind of synthesis technique of heliotrope bolt.
Background technology
Heliotropin also known as piperonal, heliotropine, chemical name is 3,4- (methylene-dioxy) benzaldehyde, and outward appearance is
White or pale yellow crystals body.Heliotropin is a kind of important fine chemicals and organic synthesis intermediate, in food, day
All it is widely used in the industries such as change, fine chemistry industry, medicine.
The synthetic method of domestic heliotropin mainly has now: the synthetic method with piperine as raw material, with Isosafrole
Element is synthetic method and three kinds of methods of total synthesis method of initiation material.Synthetic method with piperine as raw material is heliotropin
Earliest preparation method, this raw materials technology is rare, and high cost is eliminated.Safrole Fa Shi China and in the world most
The method of the production heliotropin of number country all employings, the feature of this method is that the time of industrial application is longer, in technique
More ripe, but the raw material safrole more than 90% producing heliotropin at present is to be extracted using sassafras root, thus
The resource making sassafras increasingly reduces, and substantial amounts of high alkali liquid waste water and sodium dichromate carry out oxidation reaction and heliotrope is obtained
Aldehyde has a large amount of chromate waste waters to generate in synthesis technique, serious environment pollution.Therefore, develop a kind of new synthetically prepared ocean
The method of jasminal is new problem urgently to be resolved hurrily at present.
Content of the invention
The present invention is to solve the above problems, and provides a kind of synthesis technique of heliotropin, is allowed to simple production process, operation
Easily, less energy consumption, low cost, efficiency high, suitable popularization.
The technical solution of the present invention:
A kind of synthesis technique of heliotropin, the synthesis technique of described heliotropin comprises the following steps:
(1) synthesizing section
50% quantitative glyoxalic acid and 98% acetic acid is added in synthesis reactor, and Deca 98% concentrated sulphuric acid at a certain temperature, drip
Bi Hou, Deca piperonyl cyclonene below -3 DEG C, reaction generates piperonyl cyclonene glycolic；After reaction terminates, dilute, and with liquid caustic soda
With the sulphuric acid in aqueous phase in synthesis reactor, acetic acid, glyoxalic acid etc., make ph to 6 about, intermediate product piperonyl cyclonene glycolic exists for solid
Bottom, does not react；Proceed to intensification removing piperonyl cyclonene, condensed rear layering afterwards, piperonyl cyclonene is back to synthesis reactor, recycling condensing water
In stills for air blowing and lower the temperature stand-by；
(2) oxidation section
Material is warming up to 40 DEG C, simultaneously to the sodium nitrite solution (preparation) of Deca in stills for air blowing 66% concentrated nitric acid and 6%, adjusts
The flow of two material droppings, controls temperature in the kettle within the specific limits, completion of dropping is incubated complete to piperonyl cyclonene ethanol acid reaction
Bi Hou, adds toluene to be extracted into stills for air blowing, after stratification, organic faciess Distillation recovery toluene solvant, and leftover materials turn
Enter the kettle that decolours, process with laggard sewage plant in aqueous phase liquid feeding alkali；
Add quantitative water, sodium carbonate and thiourea into decolouring kettle, be warming up to uniform temperature and be incubated some hours, be down to room temperature
Stratification afterwards, organic faciess enter rectifying column rectification, and waste water enters plant area's sewage plant and processes；After rectifying column rectification under vacuum, condensation obtains
Heliotropin crude product, enters back in refining kettle, crystallisation by cooling after adding ethanol to refine, and centrifugation post-drying obtains product heliotrope
Aldehyde.
As the optimization further of this programme, under described step (1) uniform temperature, it is less than 5 DEG C.
As control temperature in the kettle in the optimization further of this programme, described step (2) between 40 DEG C -50 DEG C.
As the optimization further of this programme, it is warming up to uniform temperature in described step (2) and is incubated some hours for rising
Temperature and is incubated 3 hours between 80 DEG C -85 DEG C.
Beneficial effects of the present invention:
1. the present invention, with piperonyl cyclonene, glyoxalic acid, nitric acid etc. as main material, obtains product heliotrope after synthesis and oxidation reaction
Aldehyde, simple production process, processing ease, less energy consumption, low cost, efficiency high, suitable popularization, and the foreign jasmine that the present invention produces
Jasmine aldehyde yield is 87% about；2. the present invention adopts three-level chilled brine to condense recycling design, toluene, ethanol, piperonyl cyclonene condensation effect
Rate is respectively 99%, 97%, 99.5%, improves the recycling of solvent, reduces and is passed through cost.
Specific embodiment
All features disclosed in this specification, or disclosed all methods or during step, except mutually exclusive
Feature and/or step beyond, all can combine by any way.
Any feature disclosed in this specification (including any accessory claim, summary), unless specifically stated otherwise,
Replaced by other alternative features equivalent or that there is similar purpose.I.e., unless specifically stated otherwise, each feature is a series of
One of equivalent or similar characteristics example.
Embodiment:
A kind of synthesis technique of heliotropin is it is characterised in that the synthesis technique of described heliotropin comprises the following steps:
(1) synthesizing section
50% quantitative glyoxalic acid and 98% acetic acid is added in synthesis reactor, and Deca 98% concentrated sulphuric acid, completion of dropping below 5 DEG C
Afterwards, Deca piperonyl cyclonene below -3 DEG C, reaction generates piperonyl cyclonene glycolic；After reaction terminates, dilute, and neutralized with liquid caustic soda
Sulphuric acid in aqueous phase in synthesis reactor, acetic acid, glyoxalic acid etc., make ph to 6 about, and intermediate product piperonyl cyclonene glycolic is solid the bottom of at
Portion, does not react；Proceeding to intensification removing piperonyl cyclonene afterwards, condensed after be layered, piperonyl cyclonene is back to synthesis reactor, recycling condensing water in
Stills for air blowing are simultaneously lowered the temperature stand-by；
(2) oxidation section
Material is warming up to 40 DEG C, simultaneously to the sodium nitrite solution (preparation) of Deca in stills for air blowing 66% concentrated nitric acid and 6%, adjusts
The flow of two material droppings, controls temperature in the kettle at 40 DEG C -50 DEG C, completion of dropping is incubated and finishes to piperonyl cyclonene ethanol acid reaction
Afterwards, toluene is added to be extracted into stills for air blowing, after stratification, organic faciess Distillation recovery toluene solvant, leftover materials proceed to
Decolouring kettle, is processed with laggard sewage plant in aqueous phase liquid feeding alkali；
Add quantitative water, sodium carbonate and thiourea into decolouring kettle, be warming up to 80 DEG C -85 DEG C and be incubated 3 hours, be down to quiet after room temperature
Put layering, organic faciess enter rectifying column rectification, waste water enters plant area's sewage plant and processes；After rectifying column rectification under vacuum, condensation obtains foreign jasmine
Jasmine aldehyde crude product, enters back in refining kettle, crystallisation by cooling after adding ethanol to refine, and centrifugation post-drying obtains product heliotropin.
The yield that the present invention is allowed to product by synthesizing section, oxidation section operation production heliotropin is 87% about, raw
Production. art is simple, processing ease, less energy consumption, low cost, efficiency high, suitable popularization.The present invention adopts three-level chilled brine to condense
Recycling design, toluene, ethanol, piperonyl cyclonene, heliotropin condensation efficiency are respectively 99%, 97%, 99.5%, improve the recovery of solvent
Using reduction is passed through cost.
The basic teaching of the present invention is illustrated, and for having the people of the usual technical ability in this area, many extends and becomes
Change will be aobvious and the person of being apparent from.Because the present invention that description discloses can be in the other spies without departing from present invention spirit or general characteristics
Setting formula is implementing, and some forms of these particular forms have been noted, so, description embodiments of the disclosure should be regarded as
Illustrate rather than restriction.The scope of the present invention is to be defined by appended claim, rather than by described above institute circle
Calmly, within the scope of all changes of the impartial meaning and scope that fall into claim still being will be contained in it.
Claims (4)
1. a kind of synthesis technique of heliotropin is it is characterised in that the synthesis technique of described heliotropin comprises the following steps:
(1) synthesizing section
50% quantitative glyoxalic acid and 98% acetic acid is added in synthesis reactor, and Deca 98% concentrated sulphuric acid at a certain temperature, drip
Bi Hou, Deca piperonyl cyclonene below -3 DEG C, reaction generates piperonyl cyclonene glycolic；After reaction terminates, dilute, and with liquid caustic soda
With the sulphuric acid in aqueous phase in synthesis reactor, acetic acid, glyoxalic acid etc., make ph to 6 about, intermediate product piperonyl cyclonene glycolic exists for solid
Bottom, does not react；Proceed to intensification removing piperonyl cyclonene, condensed rear layering afterwards, piperonyl cyclonene is back to synthesis reactor, recycling condensing water
In stills for air blowing and lower the temperature stand-by；
(2) oxidation section
Material is warming up to 40 DEG C, simultaneously to the sodium nitrite solution (preparation) of Deca in stills for air blowing 66% concentrated nitric acid and 6%, adjusts
The flow of two material droppings, controls temperature in the kettle within the specific limits, completion of dropping is incubated complete to piperonyl cyclonene ethanol acid reaction
Bi Hou, adds toluene to be extracted into stills for air blowing, after stratification, organic faciess Distillation recovery toluene solvant, and leftover materials turn
Enter the kettle that decolours, process with laggard sewage plant in aqueous phase liquid feeding alkali；
Add quantitative water, sodium carbonate and thiourea into decolouring kettle, be warming up to uniform temperature and be incubated some hours, be down to room temperature
Stratification afterwards, organic faciess enter rectifying column rectification, and waste water enters plant area's sewage plant and processes；After rectifying column rectification under vacuum, condensation obtains
Heliotropin crude product, enters back in refining kettle, crystallisation by cooling after adding ethanol to refine, and centrifugation post-drying obtains product heliotrope
Aldehyde.
2. a kind of synthesis technique of heliotropin according to claim 1 is it is characterised in that described step (1) constant temperature
Degree is lower to be less than 5 DEG C.
3. a kind of synthesis technique of heliotropin according to claim 1 is it is characterised in that control in described step (2)
Temperature in the kettle is between 40 DEG C -50 DEG C.
4. a kind of synthesis technique of heliotropin according to claim 1 is it is characterised in that heat up in described step (2)
To uniform temperature and be incubated some hours be warming up between 80 DEG C -85 DEG C and be incubated 3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610720464.9A CN106349209A (en) | 2016-08-25 | 2016-08-25 | Process for synthesizing heliotropin |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610720464.9A CN106349209A (en) | 2016-08-25 | 2016-08-25 | Process for synthesizing heliotropin |
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| CN106349209A true CN106349209A (en) | 2017-01-25 |
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| CN201610720464.9A Pending CN106349209A (en) | 2016-08-25 | 2016-08-25 | Process for synthesizing heliotropin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113173906A (en) * | 2021-04-16 | 2021-07-27 | 兄弟科技股份有限公司 | Synthesis method of piperonal |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5095128A (en) * | 1989-11-02 | 1992-03-10 | Societe Francaise Hoechst | Preparation process for piperonal |
| JPH0827144A (en) * | 1994-07-15 | 1996-01-30 | Ube Ind Ltd | Production of piperonal |
| CN1400972A (en) * | 2000-02-02 | 2003-03-05 | 宇部兴产株式会社 | Process for preparing piperonal |
| CN101659650A (en) * | 2009-09-24 | 2010-03-03 | 上海力智生化科技有限公司 | Method of preparing piperonal in one kettle way |
| CN101693706A (en) * | 2009-10-14 | 2010-04-14 | 重庆德馨香料植物开发有限公司 | High-purity piperonal production process |
| CN101774999A (en) * | 2010-01-20 | 2010-07-14 | 中国科学院山西煤炭化学研究所 | Method for synthesizing piperonal |
| CN102153537A (en) * | 2011-02-22 | 2011-08-17 | 重庆德馨香料植物开发有限公司 | Heliotropin decolorizer and preparation method of heliotropin |
-
2016
- 2016-08-25 CN CN201610720464.9A patent/CN106349209A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5095128A (en) * | 1989-11-02 | 1992-03-10 | Societe Francaise Hoechst | Preparation process for piperonal |
| JPH0827144A (en) * | 1994-07-15 | 1996-01-30 | Ube Ind Ltd | Production of piperonal |
| CN1400972A (en) * | 2000-02-02 | 2003-03-05 | 宇部兴产株式会社 | Process for preparing piperonal |
| CN101659650A (en) * | 2009-09-24 | 2010-03-03 | 上海力智生化科技有限公司 | Method of preparing piperonal in one kettle way |
| CN101693706A (en) * | 2009-10-14 | 2010-04-14 | 重庆德馨香料植物开发有限公司 | High-purity piperonal production process |
| CN101774999A (en) * | 2010-01-20 | 2010-07-14 | 中国科学院山西煤炭化学研究所 | Method for synthesizing piperonal |
| CN102153537A (en) * | 2011-02-22 | 2011-08-17 | 重庆德馨香料植物开发有限公司 | Heliotropin decolorizer and preparation method of heliotropin |
Non-Patent Citations (1)
| Title |
|---|
| 郗宏娟，高志贤，王建国: "氧气部分替代硝酸氧化脱羧合成洋茉莉醛", 《精细化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113173906A (en) * | 2021-04-16 | 2021-07-27 | 兄弟科技股份有限公司 | Synthesis method of piperonal |
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Application publication date: 20170125 |